scholarly journals Competing Reaction Pathways in Heterogeneously Catalysed Hydrogenation of Allyl Cyanide: The Chemical Nature of Surface Species

Author(s):  
Carsten Schröder ◽  
Philipp A. Haugg ◽  
Ann-Katrin Baumann ◽  
Marvin C. Schmidt ◽  
Jan Smyczek ◽  
...  
Author(s):  
Richard R. Shivers

The sinus gland is a neurohemal organ located in the crayfish eyestalk and represents a storage site for neurohormones prior to their release into the circulation. The sinus gland contains 3 classes of dense, membrane-limited granules: 1) granules measuring less than 1000 Å in diameter, 2) granules measuring 1100-1400 Å in diameter, and 3) granules measuring 1500-2000 Å in diameter. Class 3 granules are the most electron-dense of the granules found in the sinus gland, while class 2 granules are the most abundant. Generally, all granules appear to undergo similar changes during release.Release of neurosecretory granules may be initiated by a preliminary fragmentation of the “parent granule” into smaller, less dense vesicles which measure about 350 Å in diameter (V, Figs. 1-3). A decrease in density of the granules prior to their fragmentation has been observed and may reflect a change in the chemical nature of the granule contents.


Author(s):  
Nicholas J Severs

In his pioneering demonstration of the potential of freeze-etching in biological systems, Russell Steere assessed the future promise and limitations of the technique with remarkable foresight. Item 2 in his list of inherent difficulties as they then stood stated “The chemical nature of the objects seen in the replica cannot be determined”. This defined a major goal for practitioners of freeze-fracture which, for more than a decade, seemed unattainable. It was not until the introduction of the label-fracture-etch technique in the early 1970s that the mould was broken, and not until the following decade that the full scope of modern freeze-fracture cytochemistry took shape. The culmination of these developments in the 1990s now equips the researcher with a set of effective techniques for routine application in cell and membrane biology.Freeze-fracture cytochemical techniques are all designed to provide information on the chemical nature of structural components revealed by freeze-fracture, but differ in how this is achieved, in precisely what type of information is obtained, and in which types of specimen can be studied.


1998 ◽  
Vol 08 (PR5) ◽  
pp. Pr5-85-Pr5-89
Author(s):  
P. Sarrazin ◽  
F. Bernard ◽  
G. Calvarin ◽  
J. C. Niepce ◽  
B. Thierry

2019 ◽  
Author(s):  
Clare Bakewell ◽  
Martí Garçon ◽  
Richard Y Kong ◽  
Louisa O'Hare ◽  
Andrew J. P. White ◽  
...  

The reactions of an aluminium(I) reagent with a series of 1,2-, 1,3- and 1,5-dienes are reported. In the case of 1,3-dienes the reaction occurs by a pericyclic reaction mechanism, specifically a cheletropic cycloaddition, to form aluminocyclopentene containing products. This mechanism has been interrogated by stereochemical experiments and DFT calculations. The stereochemical experiments show that the (4+1) cycloaddition follows a suprafacial topology, while calculations support a concerted albeit asynchronous pathway in which the transition state demonstrates aromatic character. Remarkably, the substrate scope of the (4+1) cycloaddition includes dienes that are either in part, or entirely, contained within aromatic rings. In these cases, reactions occur with dearomatisation of the substrate and can be reversible. In the case of 1,2- or 1,5-dienes complementary reactivity is observed; the orthogonal nature of the C=C π-bonds (1,2-diene) and the homoconjugated system (1,5-diene) both disfavour a (4+1) cycloaddition. Rather, reaction pathways are determined by an initial (2+1) cycloaddition to form an aluminocyclopropane intermediate which can in turn undergo insertion of a further C=C π-bond leading to complex organometallic products that incorporate fused hydrocarbon rings.


2018 ◽  
Author(s):  
Victor Laserna ◽  
Tom Sheppard

A versatile approach to the valorization of propargylic alcohols is reported, enabling controlled access to three different products from the same starting materials. Firstly, a general method for the hydroamination of propargylic alcohols with anilines is described using gold catalysis to give 3-hydroxy imines with complete regioselectivity. These 3-hydroxyimines can be reduced to give 1,3-aminoalcohols with high syn seletivity. Alternatively, by using a catalytic quantity of aniline, 3-hydroxyketones can be obtained in high yield directly from propargylic alcohols. Further manipulation of the reaction conditions enables the selective formation of 3-aminoketones via a rearrangement/hydroamination pathway.<br>


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